Treatment of organic compounds



Patented Sept. 7, 1937 UNITED STATES PATENT OFFICE 11 Claims.

This invention relates to'improvements in the saponification of Organic esters of cellulose, and

is particularly concerned with the saponification of filaments, threads, fibres, ribbons, films and 5 like materials 'comprising such esters.

The usual method of saponifying such materials is by treatment with aqueous solutions of caustic soda. The use of caustic soda, however, in common with that of other strong mineral alkalies, presents certain disadvantages. Thus unless special methods are adopted saponification is apt to be superficial, leaving a core of substantially unchanged cellulose ester, and there is some danger of excessive-degradation of the cellulose molecule'occurring with resulting'loss of tenacity in the materials; Considerable research has therefore been carried out with a view to develop ing more satisfactory methods of saponifying such materials.

According to the present invention,in the saponification of organic esters of cellulose at least the first part of the desired,saponification iseifected with the aid of a solution containing ammonia, and a strong mineral saponifying agent is present at least during the final stages of said saponil'ication. The process is of particular importance in the treatment of filaments, threads, fibres, ribbons, filmsand like materials having a basis of cellulose acetate and will be described with particular reference thereto. The; process of the invention enables a relatively deep-seated saponification of filaments, threads,'fibres, ribbons, films and like materialshaving a basis .Of organic ester of cellulose to be effected at a rela- 3 tively rapid rate. The products of the process may exhibit a very high tenacity coupled with a good extensibility and elasticity and an'afii'nity for cotton dyes, which may or may'not be ac companied by an afiinity for cellulose ester dyes.

40 The ammonia and the mineral saponifying agent are preferably applied to the materials in conjunction. Even very small amounts of a strong mineral saponifyin'g agent, for example 1 to.2% or less of caustic soda or an equivalent of 4 other strong mineral saponifying agent are capa- 5 ammonia prior to the application of the mineral In Great Britain June 16, 1934 base. In this case the best results qua depth of saponification are obtained when a considerable proportion of the desired saponification is effected by the ammonia alone before treatment with the mineral saponifying agent. Thus it is of 5 advantage to reduce the acidyl content of the ester to 1 or even 1 acidyl group per Cal-I100: unit before treatment with the mineral saponlfying agent. Although, as indicated above, the process of 10 the invention is of particular importance in the treatment of cellulose acetate materials, the process is also applicable to the treatment of otherorganic esters of cellulose, i. e. other esters of cellulose containing organic acidyl groups. 15 Among such esters mention may be'madeof other simple esters, lower fatty acid esters, for example cellulose formate, propionate and butyrate, esters of higher fatty acids, for example cellulose laurate, mixed fatty acid esters, for example cel- 20 lulose acetate-propionate, cellulose acetate-butyr-- ate and cellulose acetate propionate-butyrate, ether-esters, for example ethyl cellulose acetate and oxy-ethyl cellulose acetate, and esters con-- taining inorganic radicles, for example nitrocel- 25 lulose acetate, nitrocellulose acetate-propionate, and nitrocellulose acetate-butyrate. The ester contentmay be that of a completely esterified cellulose. Preferably, however, materials comprising esters of intermediate ester content, for an example from 2 to 2 ester groups per molecule, are employed. In the case of cellulose acetate, for example, it is preferable to employ acetates having an acetyl value between 48 and 58%, and

"preferably between 52 and 54.5% calculated as acetic acid per CaHioOs unit. The ester may be treated in any desired form but the process is particularly'suitable for treating textile and like materials having a basis of organic ester of cellulose. The materials treat- 40 ed may be in the form of filaments, threads, yarns ribbons or the like or of fabrics containing such threads and the like. The organic ester of cellulose employed may be of 'high, normal or low viscosity. for example in the case of cellulose acetate the viscosity may be of the order of 30 to 50, 100, 200 or'even highnthese 10 January 3, 1930, 437,423 filed March 20, 1930,

469,622 filed July 21, 1930, and 601,043, filed March 24, 1932, wherein the. materials are produced by wet spinning methods in the course of which they are stretched to a considerable extent. The materials may also, particularly when spun by a dry spinning method, be subjected to a stretching treatment prior to saponification. Such treatments are particularly valuable where a high tensile strength in the products 20 is required, and for this purpose it is of ad vantage to stretch the-materials to a considerable extent, for example to 200, 300 or even more than 500% of their original length. Stretching may be facilitated by any suitable means, for example by treatment with organic swelling agents or solvents or as described in U. S. application S. Nos. 4,510 filed January 18, 1935, and 4,511 filed January 18, 1935, by treatment with steam or hot water. The stretching may be effected in a single stage or in several stages, as described in U. S. application S. No.- 573,424 filed November 6, 1931, with or without a rest interval between the stages. If desired after stretching and before saponification the materials may be treated with shrinking agents, as described for example, in U. S. application S. No. 611,240

filed May 13, 1932.

Both the ammonia and the mineral base, whether applied together or successively are pref 4 erably employed in aqueous solution. Alcoholic or aqueous-alcoholic media -may, however, be employed, and in this case at least a part of the saponification efiected may be due to the action of the alcohol upon the cellulose ester, so 45 that a greater degree of saponification occurs than could be accounted for by the amount of saponifying agent used. Apart from alcoholic compounds, among which ethyl and methyl alcohol are particularly suitable, swelling agents 50 for the cellulose ester may be present during saponification. Thus, in treating cellulose acetate materials the saponifying medium or media may contain, for example, acetone, diacetone a1- cohol, dioxane, methylene ethylene ether and 55 other cyclic ethers.

The concentration of the ammonia is prefer.- ably as high as can conveniently be employed. Thus concentrations of 30 to 45% of ammonia, e. g. 35 to 40%, can be employed with advan- 60 tage.

however be employed, for example 20 to 25% or even 15 to 20% or less, but when low concentrations are used saponification is in general somewhat protracted. On the'other hand, still 65 higher concentrations, e. g. 48% ammonia may be used. 'As indicated above the concentration of mineral alkali employed may vary considerably from 1 or 2% or less to more than 10%.

Generally speaking concentrations ,of 1 to 5% 70 have been found most suitable. The temperature of the ammonia bath whether or not this also contains a'mineral base may be relatively low, e. g. between'15 and 20 C. or even less but is preferably somewhat higher, e. g. 30 or 40 to 75 60 or 70 C. and may 'even be higher still, e. g.

Considerably lower concentrations may 'ment as a batch process.

90-100 or even above 100 C. Similar tempera- I tures may be employed in the baths containing a mineral saponifying agent when this agent is applied after the ammonia.

saponification may be effected by a continuous process, the materials being passed continuously, through a bath containing the liquid saponifying agent at such a speed that the desired degree of saponification is effected. When the materials are treated in yarn or like form it is of advantage to draw off the yarns from a creel and treat them in warp formation, i; e. in the form of a so-called warp or sheet of running threads, all guides, rollers -or like devices which determine the path of the materials extending'across the entire Warp. In some cases, for example where the nature of the saponifying agent is such that saponification is relatively slow, it is of advantage to carry out the treat- Yarns may, for example, be suspended in the form of hanks in a bath containing the saponifying agent ,or may be treated in other suitable package form, for example wound on to perforated bobbins. I

Preferably the saponification is effected in a closed vessel under superatmospheric pressure, as describedin'U. S. application S. No. 11,080 filed March 14, 1935. In this way higher concentrations of ammonia .can be used than would otherwise be possible. Saponification under pressure, although most easily carried out as a batch process may, by the use of suitable apparatus, such for example as is described in U. S. applications i S. Nos. 11,080 filed March 14, 1935, and 17,242 filed April 19, 1935, be applied to travelling materials. The pressure may be relatively small; e. g.

- from 5 lbs. or less per square inch up to an atmosphere or may be considerably higher, for instance 2-5 or 10 atmospheres or more. It is of particular advantage to provide the saponifying vessel with end pressure chambers as described in ,U. S.

application S. No. 17,242 filed- April 19, 1935.

The materials may be saponifled in fabric form.

This may conveniently be effected by passing the fabric continuously through a bath containing the saponifying agent, for example in an apparatus of the type of the winch dyeing machine. On the other hand material in fabric form may be saponified by a batch method.

The materials prior to saponification-may be subjected to a treatment adapted to facilitate the order of 10 or 15% or even less, but is pref-- erably somewhat higher, for example suflicient to produce a loss in acidyl contentof 25 or 30% up to 40% or 50% and may be higher still, for instance suflicient to reduce the acidyl content by 60-75 or 80% up to complete saponification, according to the particular purpose in View. As indicated above when a relatively high degree of Cellulose acetate'yarn is drawn in warp formetion through a closed vessel containing a 30 to 10 in excess of saponifying agent is removed, and is then dried by passage over heated rollers and collected by suitable means.

Example 2 The process is carried out as in Example 1 except that the ammoniacal saponifying medium is free from 'mineral saponifying agent. The yarn after leaving the vessel containing this medium is passed through a similar vessel con- 20 taining an aqueous solution of caustic soda of concentration 1 to 3% a? a temperature of 90- 100 C. and then to the washing, drying and collecting means.

Instead of caustic soda other mineral saponifying agents may be employed, for example caustic potash or tri-sodium phosphate.

What I claim and desire to secure by Letters Patent is:

1. Process for the saponification of organic 30 ester of cellulose, wherein at least the first part of the saponification is effected with the aid of a solution containing ammonia, and a strong mineral saponifying agent is present at least during the final stages of the desired saponification, the

solution being applied in liquid form and the conditions of treatment being such that deepseated saponification occurs.

2. Process of saponifying filaments, threads, fibres, ribbons, films and like materials having a basis of organic ester of cellulose comprising treating the same with an aqueous solution of ammonia containing a relatively small quantity of a strongv mineral saponifying agent, the solution being applied in liquid form and the conditions of treatment being such that deep-seated saponification occurs.

3. Process of saponifying filaments, threads, fibres, ribbons, films and like materials having a basis of organic ester of cellulose comprising treating the same first with an aqueous solution of ammonia, and then with a strong mineral saponifying agent, the solution being applied in liquid form and the conditions of treatment being such that deep-seated saponification occurs.

4. Process of saponifying filaments, threads, fibres, ribbons, films and like materials having a basis of cellulose acetate comprising treating the same with an aqueous solution of ammonia of concentration at least 30%, and containing 1 to of caustic soda, under pressure.

5. Process of sapom'fying. filaments, threads,

, the same first with an aqueous solution of ammonia of concentration at least 30% under pressure until the acetyl content is reduced to not more than 1 acetyl group per CsHroOs unit, and then with a 2 to 5% aqueous solution of caustic soda at a temperature above 90 C.

6. Process of saponifying filaments, threads, fibres, ribbons, films and like materials having a basis of organic ester of cellulose comprising treating the same first with an aqueous solution of ammonia until the ester contains not more than 1% acidyl groups per CsHwOs unit, and then with a strong mineral saponifying agent.

7. Process for the saponification of cellulose acetate, wherein at least the first part of the saponification is effected with the aid of a solution containing ammonia, and a strong mineral saponifying agent is present atleast during the final stages of the desired saponification, the solution being applied in liquid form and the conditions of treatment being such that deepseated saponification occurs.

8. Process of saponifying filaments, threads, fibres, ribbons, films and like materials having a basis of organic ester of cellulose comprising treating the same with an aqueous solution of ammonia containing an alkali metal hydroxide, the solution being applied in liquid form and the conditions of treatment being such that deepseated saponification occurs.

9. Process of saponifying filaments, threads, fibres, ribbons, films and like materials having a basis of cellulose acetate comprising treating the same with an aqueous solution of ammonia containing a relatively small quantity of caustic soda, the solution being applied in liquid form and the conditions of treatment being such that deep-seated saponification occurs.

10. Process of saponifying filaments, threads, fibres, ribbons, films and like materials having a basis of cellulose acetate comprising treating the same first with an aqueous solution .of ammonia, and then with an aqueous solution of an alkali metal hydroxide, the solutions being applied in liquid form and the conditions of treatment being such that deep-seated saponification occurs.

11. Process of saponifying filaments, threads, fibres, ribbons, films and like materials having a basis of cellulose acetate comprising treating the same first with an aqueous solution of ammonia until the cellulose acetate contains not more than 1 acetyl groups per C'sHioOs unit, and then with an alkalimetal hydroxide.

' HENRY DREYFUS. 

